A high-quality CIGS film with a selenization process needs to be developed for low-cost and large-scale production. In this study, we used Cu2In3, CuGa and Cu2Se sputter targets for the deposition of a precursor. The precursor deposited by sputtering was selenized in Se vapor. The precursor layer deposited by the co-sputtering of Cu2In3, CuGa and Cu2Se showed a uniform distribution of Cu, In, Ga, and Se throughout the layer with Cu, In, CuIn, CuGa and Cu2Se phases. After selenization at 550˚C for 30 min, the CIGS film showed a double-layer microstructure with a large-grained top layer and a small-grained bottom layer. In the AES depth profile, In was found to have accumulated near the surface while Cu had accumulated in the middle of the CIGS film. By adding a Cu-In-Ga interlayer between the co-sputtered precursor layer and the Mo film and adding a thin Cu2Se layer onto the co-sputtered precursor layer, large CIGS grains throughout the film were produced. However, the Cu accumulated in the middle of CIGS film in this case as well. By supplying In, Ga and Se to the CIGS film, a uniform distribution of Cu, In, Ga and Se was achieved in the middle of the CIGS film.

Cu(In,Ga)Se2(CIGS) photovoltaic thin films were electrodeposited on Mo/glass substrates with an aqueous solution containing 2 mM CuCl2, 8 mM InCl3, 20 mM GaCl3 and 8mM H2SeO3 at the electrodeposition potential of -0.6 to -1.0 V(SCE) and pH of 1.8. The best chemical composition of Cu1.05In0.8Ga0.13Se2 was found to be achieved at -0.7 V(SCE). The precursor Cu-In-Ga-Se films were annealed for crystallization to chalcopyrite structure at temperatures of 100-500˚C under Ar gas atmosphere. The chemical compositions, microstructures, surface morphologies, and crystallographic structures of the annealed films were analyzed by EPMA, FE-SEM, AFM, and XRD, respectively. The precursor Cu-In-Ga-Se grains were grown sparsely on the Mo-back contact and also had very rough surfaces. However, after annealing treatment beginning at 200˚C, the empty spaces between grains were removed and the grains showed well developed columnar shapes with smooth surfaces. The precursor Cu-In-Ga-Se films were also annealed at the temperature of 500˚C for 60 min under Se gas atmosphere to suppress the Se volatilization. The Se amount on the CIGS film after selenization annealing increased above the Se amount of the electrodeposited state and the MoSe2 phase occurred, resulting from the diffusion of Se through the CIGS film and interaction with Mo back electrode. However, the selenization-annealed films showed higher crystallinity values than did the films annealed under Ar atmosphere with a chemical composition closer to that of the electrodeposited state.

The selenization process has been a promising method for low-cost and large-scale production of high quality CIGS film. However, there is the problem that most Ga in the CIGS film segregates near the Mo back contact. So the solar cell behaves like a CuInSe2 and lacks the increased open-circuit voltage. In this study we investigated the Ga distribution in CIGS films by using the Ga2Se3 layer. The Ga2Se3 layer was applied on the Cu-In-Ga metal layer to increase Ga content at the surface of CIGS films and to restrict Ga diffusion to the CIGS/Mo interface with Ga and Se bonding. The layer made by thermal evaporation was showed to an amorphous Ga2Se3 layer in the result of AES depth profile, XPS and XRD measurement. As the thickness of Ga2Se3 layer increased, a small-grained CIGS film was developed and phase seperation was showed using SEM and XRD respectively. Ga distributions in CIGS films were investigated by means of AES depth profile. As a result, the [Ga]/[In+Ga] ratio was 0.2 at the surface and 0.5 near the CIGS/Mo interface when the Ga2Se3 thickness was 220 nm, suggesting that the Ga2Se3 layer on the top of metal layer is one of the possible methods for Ga redistribution and open circuit voltage increase.